CN102531263B - Method for treating saponified wastewater generated in production process of epoxy compound - Google Patents
Method for treating saponified wastewater generated in production process of epoxy compound Download PDFInfo
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- CN102531263B CN102531263B CN201210052714.8A CN201210052714A CN102531263B CN 102531263 B CN102531263 B CN 102531263B CN 201210052714 A CN201210052714 A CN 201210052714A CN 102531263 B CN102531263 B CN 102531263B
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Abstract
The invention relates to a method for treating saponified wastewater generated in the production process of an epoxy compound and belongs to the technical field of treatment of wastewater with high salt content. The method includes the following steps: inputting stock solution of the saponified wastewater, which is generated in the chlorohydrin saponification process, into a multi-effect evaporator to concentrate, wherein generated neutral condensate can be used as process water; inputting the concentrated saponified wastewater and concentrated sulfuric acid into a mixer to perform the reaction to generate HCl gas and mixed solution of sulfate and hydrochloric acid; inputting the mixed solution into an air flow drying tower to dry the mixed solution by hot air flow; carrying out cyclone separation on a gas phase to obtain solid sulfate powder; and condensating tail gas to obtain hydrochloric acid. Therefore, chloride ions in the saponified wastewater with high salt content are converted into the hydrochloric acid or the HCl gas which can be used as a product or a raw material; the generated sulfate can be respectively used as land plaster (CaSO4.0.5H2O), anhydrous sodium sulphate (Na2SO4) and a potash fertilizer (K2SO4); and the aim of resource utilization of the saponified wastewater generated in the production process of the epoxy compound is fulfilled.
Description
Technical field
The invention belongs to the processing technology field of high slat-containing wastewater, specifically relate to the treatment process of epoxy compounds production process saponification waste-water.
Background technology
Propylene oxide and epoxy chloropropane are all important Essential Chemistry product, and the production method of industrial extensive employing is at present all through saponification cyclization, to prepare epoxy compounds by corresponding chloropharin, and typical reaction formula is as follows:
No matter by above-mentioned reaction formula, can be found out, be to make alkali source with caustic soda or with lime, all can produce stoichiometric sodium-chlor and calcium chloride, thereby produce a large amount of brine wastes in saponification process.Different process process generation saponification waste-water amount and salt concn are as shown in table 1:
Table 1 different process process produces saponification waste-water situation
Salt and epoxy compounds all have killing action to microorganism, so the saponification waste-water that epoxy compounds production process produces is difficult to process by biochemical degradation method.
So the processing of epoxy compounds a large amount of saponification waste-waters that production process produces is the industrial a great problem facing always.In CN101531442A, propose can remove the organism (glycerine) in saponification liquor with active carbon adsorption, but the saturated extent of adsorption of gac is very low, need frequent regeneration and produce a large amount of desorption liquids, operation efficiency is low, cost is high, is not suitable for the production process of large tonnage product propylene oxide and epoxy chloropropane.In CN1800042A, propose to make the organism of metal ion and degraded form sediment and remove by the method for ionizing rays, this is mainly to Ca
2+, Mg
2+effective Deng salt, and to K
+, Na
+, Cl
-deng almost there is no effect.In CN101798154B, propose to process saponification waste-water by the method for multiple-effect evaporation, and reclaim salt (CaCl
2).Such method has good treatment effect, but because the wastewater discharge of unit product is very large, causes running cost too high.In addition, the CaCl reclaiming
2or NaCl added value is all less, thereby make treating processes lack the market competitiveness.
Summary of the invention
object of the present inventionbe to provide a kind of process for treating saponification wastewater efficiently with industrial competitiveness, the above-mentioned defect existing to overcome prior art.
technical scheme:
The present invention is achieved through the following technical solutions.
A treatment process for epoxy compounds production process saponification waste-water, according to following step, carry out:
(1) in the saponification waste-water stoste input multi-effect evaporation system saponification of epoxy compounds production process being produced, be concentrated into finite concentration, the neutral lime set of generation can be made process water and use;
(2) during the saponification waste-water after concentrated is inputted together with the vitriol oil and react in mixing tank, generate the mixture of HCl gas, vitriol and hydrochloric acid;
(3) will in the mixture input airstream drying tower of above-mentioned vitriol and hydrochloric acid, with hot gas flow, be dried, gas phase obtains solid sulfate salt powder through cyclonic separation, and tail gas obtains hydrochloric acid through condensation;
Wherein the described saponification waste-water stoste of step (1), is characterized in that its salt concn is at 8～25%(mass ratio), the kind of institute's saliferous is NaCl, KCl or CaCl
2, the pH value of saponification waste-water stoste is 10～14.
Wherein the described multi-effect evaporation system of step (1) is 3～5 effects, can determine effect number according to saponification waste-water stoste salt concn.Wherein the concentration of the described concentrated after saponification waste liquid of step (1) after concentrated is controlled the kind depending on salt; For the concentrated waste water salt concn containing NaCl, should be controlled at 32～35%(mass ratio); For containing CaCl
2concentrated waste water salt concn should be controlled at 48～50%(mass ratio); For the concentrated waste water salt concn containing KCl, should be controlled at 52～55%(mass ratio).
Wherein the described vitriol oil of step (2) refers to mass concentration 92～98%(mass ratio) sulfuric acid; The consumption of the vitriol oil should equal the equivalents summation of salt and free alkali in concentrated saponification waste liquid.
The HCl gas that wherein the concentrated saponification waste liquid described in step (2) and vitriol oil hybrid reaction process produce can absorb and become commodity concentrated hydrochloric acid by water, or in glycerine method epoxy chloropropane, directly gets back to technological process for the preparation of glycerin dichlorohydrin;
Wherein the described airstream drying tower of step (3) should be used warm air convection drying; For different vitriol, suitable service temperature is different; For calcium sulfate mixed solution, air stream drying temperature should, at 155～165 ℃, obtain gesso (CaSO by cyclonic separation
40.5H
2o); For K
2sO
4mixed solution, air stream drying temperature should be controlled at 520～540 ℃, by cyclonic separation, obtains anhydrous potassium sulfate (potash fertilizer); For sodium sulfate mixed solution, air stream drying temperature should be controlled at 450～500 ℃, by cyclonic separation, obtains anhydrous sodium sulphate (Sodium sulfate anhydrous.min(99)); The tail gas flowing out from cyclonic separator obtains concentrated hydrochloric acid after heat recuperation and condensation, and condensing temperature should be controlled at 15～20 ℃.
the effect of invention:the present invention program's enforcement, the saponification waste-water that epoxy compounds production process is produced is realized recycling.Wherein: the solidifying water of the concentrated neutrality steaming can be used as process water and recycles; Alkali in concentrated saponification waste-water and chlorination salt by with strong sulfuric acid response, chlorion changes into can make hydrochloric acid or the HCl gas that product or raw material are used; The vitriol generating can be respectively as terra alba (CaSO
40.5H
2o), Sodium sulfate anhydrous.min(99) (Na
2sO
4), potash fertilizer (K
2sO
4) sell.Especially to glycerine method epoxy chloropropane technological process, the HCl of recovery and hydrochloric acid can be used as the raw material of glycerin chlorination, realize utilization of wastewater resource.By the present invention program's enforcement, for the processing of saponification waste-water provides a kind of method that simply has industrial competitiveness.
Accompanying drawing explanation
The treatment process of a kind of epoxy compounds production process of the present invention saponification waste-water adopts the schematic flow sheet of device, wherein 1 saponification waste-water stoste; 2 heating steams; 3 neutral solidifying water; 4-x vaporizer (x is multiple-effect progression); 5-x vapour liquid separator (x is multiple-effect progression); 6 vacuum systems; 7 concentrated saponification waste-waters; 8 sulfuric acid; In 9 and mixing tank; 10 gas-liquid separators; 11 acid gas water coolers; 12 HCl gases; 13 sulfate mixtures; 14 vitriol transferpumps; 15 airstream drying towers; 16 cyclonic separators; 17 hot gas flows; 18 hot gas flow energy recovery and condenser systems; 19 condensation hydrochloric acid; 20 solid sulfate salt.
concrete embodiment
Embodiment 1
Derive from glycerine method epoxy chloropropane technological process, take KOH as alkali source.
Open vacuum system
6, saponification waste-water stoste
1(365 ㎏/h) (its composition is 1.2%KOH, 0.52% glycerine, 0.16% organic chloride, 23.8%KCl(mass ratio)) and the heating steam of 168 ℃
2(66 ㎏/h) input triple effect evaporation system is (by vaporizer
4-1,4-2,4-3and vapour liquid separator
5-1,5-2,5-3form), produce neutral solidifying water
3(269 ㎏/h), the concentrated saponification waste-water of output
7(162 ㎏/h), wherein contains: 2.5%KOH, 1.42% glycerine, 53.8%KCl, 0.08% organic chloride (mass ratio).
Above-mentioned concentrated saponification waste-water
7in input and mixing tank
9, with the vitriol oil (98%)
8(62 ㎏/h) reaction.Mixed reactant is through gas-liquid separator
10separation, produces gas phase through acid gas water cooler
11condensation discharges HCl gas
12(19.7 ㎏/h), and form hydrochloric and K
2sO
4sulfate mixture
13(204.3 ㎏/h).
Above-mentioned sulfate mixture
13use vitriol transferpump
14directly input airstream drying tower
15in, with 520 ℃ of hot gas flows
17dry.Pressed powder is through cyclonic separator
16obtain solid sulfate salt
20(K
2sO
4) dry powder (106.8 ㎏/h), can directly as potash fertilizer, use.Exhaust gas heat flowed energy reclaims and condenser system
18obtain condensation hydrochloric acid
19(97.5 ㎏/h) is (wherein containing 23.6%HCl, 2.36% glycerine, 0.2%K
2sO
4, 0.15% other organism) (mass ratio).The HCl gas (19.7 ㎏/h) that this hydrochloric acid and above-mentioned neutralization reaction process produce is got back in the lump glycerin chlorination workshop section and is used as raw material.
Embodiment 2:
Derive from propylene high-temperature chlorination process epoxy chloropropane technique.Rare chloropharin liquid (containing 4.7% dichlorohydrin (mass ratio)), is solvent with 1,2-ethylene dichloride, after solids removed by filtration thing, obtains the saponification waste-water of clarification.After counter-current extraction, take lime as saponification alkali source.
Open vacuum system
6, saponification waste-water stoste
1(360 ㎏/h) (its composition is Ca (OH)
2: 3.8%, CaCl
2: 18.6%, glycerine 0.58%, organic chloride 0.11%(mass ratio)) and the heating steam of 168 ℃
2(78 ㎏/h) input four-effect evaporator system is (by vaporizer
4-1,4-2,4-3,4-4and vapour liquid separator
5-1,5-2,5-3,5-4form), produce neutral solidifying water
3(302 ㎏/h), the concentrated saponification waste-water of output
7(136 ㎏/h), wherein contains: 8.7% Ca (OH)
2, 49.5% CaCl
2, 1.68% glycerine, 0.07% organic chloride.(mass ratio).
Above-mentioned concentrated saponification waste-water
7in input and mixing tank
9, in mixing tank and sulfuric acid
8(92%) (82 ㎏/h) reaction.Mixed reactant is through gas-liquid separator
10separation, produces gas phase through acid gas water cooler
11condensation discharges HCl gas
12(24.5 ㎏/h), and form hydrochloric and CaSO
4sulfate mixture
13(193.5 ㎏/h).
Above-mentioned sulfate mixture
13use vitriol transferpump
14directly input airstream drying tower
15in, with 165 ℃ of hot gas flows
17dry.Pressed powder is through cyclonic separator
16separation obtains solid sulfate salt
20(gesso) (114.5 ㎏/h).Tail gas is through hot gas flow energy recovery and condenser system
18obtain condensation hydrochloric acid
19(79 ㎏/h) (containing 24.9%HCl(mass ratio)).
Embodiment 3:
Derive from allyl acetate method epoxy chloropropane technique, take caustic soda as alkali source.
Open vacuum system
6, saponification waste-water stoste
1the heating steam of (360 ㎏/h) (its composition is 0.8%NaOH, 8.9%NaCl, 0.37% glycerine, 0.19% organic chloride (mass ratio)) and 168 ℃
2(71.5 ㎏/h) inputs five effect vapo(u)rization systems (by vaporizer
4-1,4-2,4-3,4-4,4-5and vapour liquid separator
5-1,5-2,5-3,5-4,5-5form), produce neutral solidifying water
3(335 ㎏/h), the concentrated saponification waste-water of output
7(96.5 ㎏/h), wherein contains: 2.9%NaOH, 33.2%NaCl, 1.43% glycerine, 0.36% organic chloride (mass ratio).
Above-mentioned concentrated saponification waste-water
7in input and mixing tank
9, in mixing tank and sulfuric acid
8(96%) (31.5 ㎏/h) reaction.Mixed reactant is through gas-liquid separator
10separation, produces gas phase through acid gas water cooler
11condensation total reflux and without HCl gas
12discharge, form hydrochloric and Na
2sO
4sulfate mixture
13(128 ㎏/h).
Said mixture
13use vitriol transferpump
14directly input airstream drying tower
15in, with 480 ℃ of hot gas flows
17dry.Pressed powder is through cyclonic separator
16separation obtains solid sulfate salt
20(Sodium sulfate anhydrous.min(99)) (44 ㎏/h).Tail gas is through hot gas flow energy recovery and condenser system
18obtain condensation hydrochloric acid
19(84 ㎏/h) (containing 23.8%HCl(mass ratio)).
Embodiment 4:
Derive from producing propylene oxide by chlorohydrination method technique, saponification waste-water, after solids is removed in sedimentation, obtains the saponification waste-water of clarification.Take lime as saponification alkali source.
Open vacuum system
6, saponification waste-water stoste
1(360 ㎏/h) (its composition is Ca (OH)
2: 2.1%, CaCl
2: 8.1%, propylene glycol 0.36%, organic chloride 0.12%(mass ratio)) and the heating steam of 168 ℃
2(85 ㎏/h) inputs five effect vapo(u)rization systems (by vaporizer
4-1,4-2,4-3,4-4,4-5and vapour liquid separator
5-1,5-2,5-3,5-4,5-5form), produce neutral solidifying water
3(388 ㎏/h), the concentrated saponification waste-water of output
7(57 ㎏/h), wherein contains: Ca (OH)
212.9%, CaCl
251.3%, propylene glycol 1.69%, organic chloride 0.17%(mass ratio).
Above-mentioned concentrated saponification waste-water
7in input and mixing tank
9, in mixing tank and sulfuric acid
8(98%) (36 ㎏/h) reaction.Mixed reactant is through gas-liquid separator
10separation, produces gas phase through acid gas water cooler
11condensation discharges HCl gas
12(12.5 ㎏/h), and form hydrochloric and CaSO
4sulfate mixture
13(80.5 ㎏/h).
Above-mentioned sulfate mixture
13use vitriol transferpump
14directly input airstream drying tower
15in, with 165 ℃ of hot gas flows
17dry.Pressed powder is through cyclonic separator
16separation obtains solid sulfate salt
20(gesso) (52.5 ㎏/h).Tail gas is through hot gas flow energy recovery and condenser system
18obtain condensation hydrochloric acid
19(28 ㎏/h) (containing 23.2%HCl(mass ratio)).
Claims (1)
1. a treatment process for epoxy compounds production process saponification waste-water, is characterized in that carrying out according to following step:
(1) in the saponification waste-water stoste input multi-effect evaporation system saponification of epoxy compounds production process being produced, be concentrated into finite concentration, the neutral lime set of generation can be made process water and use;
(2) during the saponification waste-water after concentrated is inputted together with the vitriol oil and react in mixing tank, generate the mixture of HCl gas, vitriol and hydrochloric acid;
(3) will in the mixture input airstream drying tower of above-mentioned vitriol and hydrochloric acid, with hot gas flow, be dried, gas phase obtains solid sulfate salt powder through cyclonic separation, and tail gas obtains hydrochloric acid through condensation;
The described saponification waste-water stoste of step (1) wherein, the quality that it is characterized in that its salt is than concentration 8～25%, and the kind of institute's saliferous is NaCl, KCl or CaCl
2, the pH value of saponification waste-water stoste is 10～14;
Wherein the described multi-effect evaporation system of step (1) is 3～5 effects, can determine effect according to saponification waste-water stoste salt concn
Number;
Wherein the concentration of the described concentrated after saponification waste liquid of step (1) after concentrated is controlled the kind depending on salt; For the concentrated waste water salt concn containing NaCl, should be controlled at mass ratio 32～35%; For containing CaCl
2concentrated waste water salt concn be controlled at mass ratio 48～50%; For the concentrated waste water salt concn containing KCl, should be controlled at mass ratio 52～55%;
Wherein the described vitriol oil of step (2) refers to the sulfuric acid of mass concentration 92～98%; The consumption of the vitriol oil should equal the equivalents summation of salt and free alkali in concentrated saponification waste liquid;
The HCl gas that wherein the concentrated saponification waste liquid described in step (2) and vitriol oil hybrid reaction process produce can absorb and become commodity concentrated hydrochloric acid by water, or in glycerine method epoxy chloropropane, directly gets back to technological process for the preparation of glycerin dichlorohydrin;
Wherein the described airstream drying tower of step (3) should be used warm air convection drying; For different vitriol, suitable service temperature is different; For calcium sulfate mixed solution, air stream drying temperature should, at 155～165 ℃, obtain gesso CaSO by cyclonic separation
40.5H
2o; For K
2sO
4mixed solution, air stream drying temperature should be controlled at 520～540 ℃, by cyclonic separation, obtains anhydrous potassium sulfate; For sodium sulfate mixed solution, air stream drying temperature should be controlled at 450～500 ℃, by cyclonic separation, obtains anhydrous sodium sulphate; The tail gas flowing out from cyclonic separator obtains concentrated hydrochloric acid after heat recuperation and condensation, and condensing temperature should be controlled at 15～20 ℃.
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| CN106395979B (en) * | 2016-12-09 | 2019-06-11 | 大连凯泓科技有限公司 | Cyclonic separation water treatment facilities and method for treating water |
| CN108275843A (en) * | 2018-02-27 | 2018-07-13 | 河南君和环保科技有限公司 | A kind of acrylonitrile-chlorinated method production epoxychloropropane waste water integrated treatment process of high temperature |
| CN111470526A (en) * | 2020-04-03 | 2020-07-31 | 安徽科安废盐资源化有限公司 | Method for producing hydrochloric acid-liquid caustic soda-composite material by using industrial waste miscellaneous salt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374256A (en) * | 2001-03-09 | 2002-10-16 | 肖藻生 | Waste alkali liquor oxidizing, decomposing, neutralizing and saponifying treatment with cyclohexane |
| CN101012499A (en) * | 2007-02-05 | 2007-08-08 | 扬州大学 | Method for separating highly-pure rare-earth oxide from sulphating roasting rare earth mine |
| CN101880782A (en) * | 2010-01-06 | 2010-11-10 | 马克印 | Process for rare-earth smelting resource reclamation and cyclic production |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374256A (en) * | 2001-03-09 | 2002-10-16 | 肖藻生 | Waste alkali liquor oxidizing, decomposing, neutralizing and saponifying treatment with cyclohexane |
| CN101012499A (en) * | 2007-02-05 | 2007-08-08 | 扬州大学 | Method for separating highly-pure rare-earth oxide from sulphating roasting rare earth mine |
| CN101880782A (en) * | 2010-01-06 | 2010-11-10 | 马克印 | Process for rare-earth smelting resource reclamation and cyclic production |
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